JPH0730148B2 - Method for producing polymer having formaldehyde as constitutional unit - Google Patents
Method for producing polymer having formaldehyde as constitutional unitInfo
- Publication number
- JPH0730148B2 JPH0730148B2 JP60198750A JP19875085A JPH0730148B2 JP H0730148 B2 JPH0730148 B2 JP H0730148B2 JP 60198750 A JP60198750 A JP 60198750A JP 19875085 A JP19875085 A JP 19875085A JP H0730148 B2 JPH0730148 B2 JP H0730148B2
- Authority
- JP
- Japan
- Prior art keywords
- formaldehyde
- polymer
- compound
- constituent unit
- copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
- C08G2/06—Catalysts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
- C08G2/08—Polymerisation of formaldehyde
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
- C08G2/18—Copolymerisation of aldehydes or ketones
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Polyethers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はホルムアルデヒドを構成単位とするポリマーの
製造方法に関するものである。TECHNICAL FIELD The present invention relates to a method for producing a polymer having formaldehyde as a constituent unit.
ホルムアルデヒドを構成単位とするポリマーの製造方法
は種々公知であり、松島著，プラスチック材料講座13巻
「ポリアセタール樹脂」等に総説されている。ホルムア
ルデヒドを構成単位とするポリマーは優れた機械的諸特
性を有している故に広く普及されているが、ホルムアル
デヒドの反応性が極めて高い為に、人為的な反応のコン
トロールは難しく、製造される分子量分布は広く、ブロ
ックコポリマーのブロックの配列の制御も極めて困難が
伴う。Various methods for producing a polymer having formaldehyde as a constituent unit are known, and are reviewed in Matsushima, Plastic Material Course, Vol. 13, "Polyacetal Resin" and the like. Polymers containing formaldehyde as a constituent unit are widely used because of their excellent mechanical properties.However, since the reactivity of formaldehyde is extremely high, it is difficult to control the artificial reaction, and the molecular weight produced The distribution is wide, and it is extremely difficult to control the arrangement of blocks in the block copolymer.
本発明者らはホルムアルデヒドを構成単位とするポリマ
ーの反応が制御可能であれば、ホルムアルデヒドを構成
単位とするポリマーの機械的諸特性の制御が可能にな
り、極めて広い応用範囲が得られることに着目して鋭意
研究に取り組んだ。その結果、ホルムアルデヒドを構成
単位とするポリマーの重合に際して、テトラフェニルポ
ルフィリンもしくはその誘導体と特定の有機金属化合物
を反応させて得られる錯体を触媒に使用すれば、得られ
るポリマーは分子量分布が狭く、ブロックコポリマーの
ブロックの配列も任意に設計が可能であることを見出
し、本発明を完成するに至った。The present inventors have noticed that if the reaction of a polymer containing formaldehyde as a constituent unit can be controlled, it becomes possible to control various mechanical properties of a polymer containing formaldehyde as a constituent unit, and an extremely wide range of applications can be obtained. I worked hard on my research. As a result, when a polymer obtained by reacting tetraphenylporphyrin or its derivative with a specific organometallic compound is used as a catalyst during the polymerization of a polymer having formaldehyde as a constitutional unit, the obtained polymer has a narrow molecular weight distribution, The inventors have found that the block arrangement of the copolymer can be designed arbitrarily, and have completed the present invention.
即ち、本発明は、テトラフェニルポルフィリンもしくは
その誘導体と２価又は３価の原子価を持つ金属の有機金
属化合物とを反応させて得られる錯体を触媒とすること
を特徴とするホルムアルデヒドを構成単位とするポリマ
ーの製造方法に関するものである。That is, the present invention uses formaldehyde, which is characterized by using a complex obtained by reacting tetraphenylporphyrin or a derivative thereof with an organometallic compound of a metal having a divalent or trivalent valence as a structural unit. The present invention relates to a method for producing a polymer.
本発明で使用されるテトラフェニルポルフィリンもしく
はその誘導体はベンズアルデヒドもしくはその誘導体及
びピロールを反応させて得られる。The tetraphenylporphyrin or its derivative used in the present invention can be obtained by reacting benzaldehyde or its derivative with pyrrole.
本発明において、有機金属化合物としては２価又は３価
の原子価を持つ金属の化合物が好ましく使用でき、亜
鉛、マグネシウム、アルミニウム等の金属化合物が好ま
しい例であり、有機アルミニウム化合物が特に好まし
い。具体的には、ジエチルアルミニウムクロライド及び
トリエチルアルミニウムが例示される。後者の場合は更
にアニオン種として活性水素を持つ化合物類、アルコー
ル、カルボン酸、フェノール、スルホン酸化合物等を反
応させて使用することができる。In the present invention, a compound of a metal having a divalent or trivalent valence can be preferably used as the organometallic compound, and a metal compound such as zinc, magnesium or aluminum is a preferred example, and an organoaluminum compound is particularly preferred. Specifically, diethyl aluminum chloride and triethyl aluminum are exemplified. In the latter case, compounds having active hydrogen as anion species, alcohols, carboxylic acids, phenols, sulfonic acid compounds and the like can be further reacted and used.
本発明の錯体触媒には、通常の配位子類の使用が可能で
ある。これらの配位子類は３級アミン類、ホスフィン
類、ホスファイト類、チアゾリウム類等である。中でも
特に好ましい例はイミダゾール誘導体類である。これら
配位子の使用は分子量分布を更に狭くする。配位子の添
加量は金属ポルフィリン1mole当たり0.1乃至3.0mole使
用可能であるが、好ましくは0.5乃至2.0moleであり、特
に好ましくは0.8乃至1.5moleである。Usual ligands can be used in the complex catalyst of the present invention. These ligands are tertiary amines, phosphines, phosphites, thiazolium and the like. Among them, particularly preferable examples are imidazole derivatives. The use of these ligands further narrows the molecular weight distribution. The amount of the ligand added may be 0.1 to 3.0 moles per 1 mole of metalloporphyrin, preferably 0.5 to 2.0 moles, particularly preferably 0.8 to 1.5 moles.
本発明で用いるホルムアルデヒドを構成単位とするポリ
マーとしてはホルムアルデヒドのホモポリマー又はコポ
リマーであり、ホルムアルデヒドを構成単位とするコポ
リマーのホルムアルデヒド以外の構成単位は、アルキレ
ンオキサイド、ラクトン、カルボン酸環状無水物、二酸
化炭素の内より選ばれる１種もしくは２種以上の化合物
であり、好ましくはアルキレンオキサイド類であり、特
に好ましいものは下記一般式（Ｉ）又は（II）で表わさ
れる、化合物の炭素数が９以下のエポキシ環を有する化
合物である。The polymer having formaldehyde as a constituent unit used in the present invention is a homopolymer or copolymer of formaldehyde, and the constituent unit other than formaldehyde in the copolymer having formaldehyde as a constituent unit is alkylene oxide, lactone, carboxylic acid cyclic anhydride, carbon dioxide. One or more compounds selected from among the above, preferably alkylene oxides, and particularly preferred are those represented by the following general formula (I) or (II), in which the compound has 9 or less carbon atoms. It is a compound having an epoxy ring.
（式中、R1〜R8は、各々水素原子又は炭化水素基であ
り、R1〜R4のいずれか２つが連続した環構造をとっても
良い。） これらの内、特に好ましい例はエチレンオキサイドであ
る。 (In the formula, R 1 to R 8 are each a hydrogen atom or a hydrocarbon group, and any two of R 1 to R 4 may have a continuous ring structure.) Of these, particularly preferred examples are ethylene oxide. Is.
本発明で使用されるホルムアルデヒドは、パラホルムア
ルデヒド、トリオキサン等を分解して得られる分子状ホ
ルムアルデヒドが好ましく、形態はガス状もしくは液状
のいずれでも使用できる。何れの場合も使用するホルム
アルデヒドは通常の方法で乾燥する必要がある。The formaldehyde used in the present invention is preferably molecular formaldehyde obtained by decomposing paraformaldehyde, trioxane and the like, and the form may be either gaseous or liquid. In either case, the formaldehyde used must be dried in the usual way.
本発明で使用される溶媒は、ベンゼン、トルエン、キシ
レン等の炭化水素、塩化メチレン、クロロホルム、ジク
ロルエタン等のハロゲン系炭化水素が用いられる。As the solvent used in the present invention, hydrocarbons such as benzene, toluene and xylene, and halogen-based hydrocarbons such as methylene chloride, chloroform and dichloroethane are used.
本発明の重合は、テトラフェニルポルフィリンもしくは
その誘導体と有機金属化合物を不活性ガスの雰囲気下、
溶媒の存在下に反応させて錯体触媒を生じさせ、これに
ホルムアルデヒドを加え重合を行うか、又はアルキレン
オキサイド、ラクトン、カルボン酸環状無水物、二酸化
炭素の内の１種もしくは２種以上の化合物を加えプレポ
リマーを得た後に速やかにホルムアルデヒドを加え反応
を行うが、これを繰り返すことによってブロック数を増
やすことも可能である。使用する構成単位の使用量と繰
り返し回数を制御することが可能であるので、任意のブ
ロック長と、ブロックの繰り返し数が設計できる。ブロ
ックコポリマーの各ブロックのモノマーの使用割合は任
意に選択できる。Polymerization of the present invention, tetraphenylporphyrin or a derivative thereof and an organometallic compound in an atmosphere of an inert gas,
A complex catalyst is formed by reacting in the presence of a solvent, and formaldehyde is added to this to perform polymerization, or one or more compounds selected from alkylene oxide, lactone, carboxylic acid cyclic anhydride, and carbon dioxide are added. In addition, formaldehyde is added immediately after the prepolymer is obtained to carry out the reaction, but the number of blocks can be increased by repeating this. Since it is possible to control the usage amount of the constituent unit to be used and the number of repetitions, it is possible to design an arbitrary block length and the number of block repetitions. The use ratio of the monomer of each block of the block copolymer can be arbitrarily selected.
本発明により得られたポリマーは分子量が揃った分子量
分布の狭いものであり、コポリマーは意図した繰り返し
単位のものであった。The polymer obtained by the present invention had a uniform molecular weight and a narrow molecular weight distribution, and the copolymer had an intended repeating unit.
本発明のホルムアルデヒドを構成単位とするポリマーの
製造方法は重合度の極めて低いオリゴマーの製造方法と
しても使用が可能である。The method for producing a polymer having formaldehyde as a constituent unit of the present invention can be used as a method for producing an oligomer having an extremely low degree of polymerization.
本発明で得られるポリマー及びオリゴマーは非イオン界
面活性剤、分散染料、ポリウレタンなどの原料として、
又、マクロモノマーとして硬化性の塗料、レジスト原料
として使用可能である。又、他の化合物の分子量及び分
子量分布の測定の為の標準試料としても使用可能であ
る。The polymers and oligomers obtained in the present invention are used as raw materials for nonionic surfactants, disperse dyes, polyurethanes, etc.
Further, it can be used as a curable coating material as a macromonomer and a resist raw material. It can also be used as a standard sample for measuring the molecular weight and molecular weight distribution of other compounds.
以下、実施例をもって本発明を概説するが、本発明の範
囲がこれらの実施例によって規定されるものではない。Hereinafter, the present invention will be outlined with reference to examples, but the scope of the present invention is not limited by these examples.
実施例１ ベンズアルデヒド80ml（84.8g）とピロール56ml（53.6
g）をプロピオン酸3lに入れて30分間還流下に反応させ
１昼夜放置した。混合物を濾過した後、メタノール−ク
ロロホルム混合溶媒で再結晶精製してα，β，γ，δ−
テトラフェニルポルフィリンを収率20％で取得した。Example 1 Benzaldehyde 80 ml (84.8 g) and pyrrole 56 ml (53.6
g) was added to 3 liters of propionic acid, reacted for 30 minutes under reflux, and left for one day. After the mixture was filtered, it was recrystallized and purified with a mixed solvent of methanol-chloroform to obtain α, β, γ, δ-.
Tetraphenylporphyrin was obtained with a yield of 20%.
ジエチルアルミニウムクロライド0.12gと、α，β，
γ，δ−テトラフェニルポルフィリン0.61gとを乾燥窒
素雰囲気下、塩化メチレン溶媒20mlの存在下、室温で反
応させて錯体触媒0.68gを含有する触媒溶液20mlを調整
した。Diethyl aluminum chloride 0.12g, α, β,
0.61 g of γ, δ-tetraphenylporphyrin was reacted at room temperature in the presence of 20 ml of methylene chloride solvent under a dry nitrogen atmosphere to prepare 20 ml of a catalyst solution containing 0.68 g of the complex catalyst.
テトラフェニルポルフィリン錯体触媒溶液20mlに、塩化
メチレン溶媒20mlを更に加え、これに乾燥した液状のホ
ルムアルデヒドを塩化メチレンに溶解した溶液を３日間
に分けて導入し、室温で窒素雰囲気下に重合した。重合
停止後、濾別分離し、その後、末端アセチル化を行い、
分子量分布と融点を測定した。20 ml of a methylene chloride solvent was further added to 20 ml of the tetraphenylporphyrin complex catalyst solution, and a solution of dried liquid formaldehyde in methylene chloride was introduced into the solution over 3 days, and the mixture was polymerized at room temperature under a nitrogen atmosphere. After termination of polymerization, the product was separated by filtration, and then acetylated at the end,
The molecular weight distribution and melting point were measured.
結果を表１に示す。The results are shown in Table 1.
実施例２ 実施例１と同様にして得た錯体触媒1mmolに溶媒として
塩化メチレン20mlを加える。これに精製したエチレンオ
キサイド15mmolを加え、室温で窒素雰囲気下に24時間反
応させた後、直ちに液体ホルムアルデヒドを実施例１と
同様にして反応させた。その後、再びエチレンオキサイ
ド15mmolを加え24時間反応させた。重合後、実施例１と
同様にして得た結果を表１に示す。ブロック組成比はNM
Rの値より算定した。Example 2 20 ml of methylene chloride as a solvent is added to 1 mmol of the complex catalyst obtained in the same manner as in Example 1. Purified ethylene oxide (15 mmol) was added thereto, and the mixture was reacted at room temperature under a nitrogen atmosphere for 24 hours, and then liquid formaldehyde was immediately reacted in the same manner as in Example 1. Then, 15 mmol of ethylene oxide was added again and the reaction was carried out for 24 hours. Table 1 shows the results obtained in the same manner as in Example 1 after the polymerization. Block composition ratio is NM
Calculated from the value of R.
実施例３ エチレンオキサイドを第１回目、第２回目共に30mmol使
用した以外は実施例２と同様にしてブロックコポリマー
を製造した。重合後、実施例１と同様にして得た結果を
表１に示す。Example 3 A block copolymer was produced in the same manner as in Example 2 except that 30 mmol of ethylene oxide was used both in the first and second times. Table 1 shows the results obtained in the same manner as in Example 1 after the polymerization.
実施例４ 実施例１と同様にして得た錯体溶液中に気化したホルム
アルデヒドを導入させて反応させた。重合後、実施例１
と同様に分子量分布と融点を測定した。結果を表１に示
す。Example 4 Vaporized formaldehyde was introduced into the complex solution obtained in the same manner as in Example 1 and reacted. After polymerization, Example 1
Similarly, the molecular weight distribution and melting point were measured. The results are shown in Table 1.
実施例５ 実施例１と同様にして得た錯体触媒1mmolを含む溶液中
に、１−メチルイミダゾール1.2mmolを添加し、室温に
て３時間反応させた後に実施例１と同様の方法で重合を
行った。重合後、実施例１と同様に分子量分布と融点を
測定した。結果を表１に示す。Example 5 To a solution containing 1 mmol of the complex catalyst obtained in the same manner as in Example 1, 1.2 mmol of 1-methylimidazole was added, reacted at room temperature for 3 hours, and then polymerized in the same manner as in Example 1. went. After the polymerization, the molecular weight distribution and melting point were measured as in Example 1. The results are shown in Table 1.
比較例１ ステンレス製オートクレーブに乾燥したトリオキサン97
重量部、エチレンオキサイド３重量部、分子量調節剤と
してメチラール0.03重量部を加え、温度80℃窒素雰囲気
下に触媒としてBF3を加えて重合した。得られたポリマ
ーは実施例１と同様にして分子量分布と融点を測定し
た。結果を表１に示す。Comparative Example 1 Trioxane 97 dried in a stainless steel autoclave
By weight, 3 parts by weight of ethylene oxide and 0.03 part by weight of methylal as a molecular weight modifier were added, and BF 3 was added as a catalyst under a nitrogen atmosphere at a temperature of 80 ° C. for polymerization. The polymer obtained was measured for molecular weight distribution and melting point in the same manner as in Example 1. The results are shown in Table 1.
実施例６〜９ 触媒を構成する有機金属化合物として、実施例１におけ
るジエチルアルミニウムクロライドに代えてジエチル亜
鉛又はジエチルマグネシウムを使用し、実施例１と同様
にして触媒を調製し、実施例１又は２と同様に重合を行
い、評価した。結果を表２に示す。 Examples 6 to 9 As the organometallic compound constituting the catalyst, diethyl zinc or diethyl magnesium was used in place of the diethyl aluminum chloride in Example 1, and a catalyst was prepared in the same manner as in Example 1 to obtain Example 1 or 2. Polymerization was performed and evaluated in the same manner as in. The results are shown in Table 2.
Claims (7)
誘導体と２価又は３価の原子価を持つ金属の有機金属化
合物とを反応させて得られる錯体を触媒とすることを特
徴とするホルムアルデヒドを構成単位とするポリマーの
製造方法。1. A formaldehyde-containing structural unit comprising a complex obtained by reacting tetraphenylporphyrin or a derivative thereof with an organometallic compound having a divalent or trivalent valence as a catalyst. Method for producing polymer.
アルミニウムの金属化合物である特許請求の範囲第１項
記載の製造方法。2. The production method according to claim 1, wherein the organometallic compound is a metallic compound of zinc, magnesium or aluminum.
である特許請求の範囲第２項記載の製造方法。3. The method according to claim 2, wherein the organometallic compound is an organoaluminum compound.
ーが、ホルムアルデヒドのホモポリマーか、又はホルム
アルデヒドとアルキレンオキサイド、ラクトン、カルボ
ン酸環状無水物、二酸化炭素の内より選ばれる１種もし
くは２種以上の化合物とからなるコポリマーである特許
請求の範囲第１項記載の製造方法。4. A polymer having formaldehyde as a constituent unit is a homopolymer of formaldehyde, or one or more compounds selected from formaldehyde and alkylene oxides, lactones, carboxylic acid cyclic anhydrides, and carbon dioxide. The method according to claim 1, which is a copolymer consisting of
マーを製造するに際して、任意の順番でモノマーを添加
して反応させることにより、該モノマー残基よりなるブ
ロックの配列を任意に制御する特許請求の範囲第４項記
載の製造方法。5. A method for producing a copolymer having formaldehyde as a constituent unit, wherein monomers are added in any order and reacted to arbitrarily control the sequence of blocks consisting of the monomer residues. 4. The manufacturing method according to item 4.
ーがホルムアルデヒドとアルキレンオキサイドからなる
コポリマーである特許請求の範囲第４項記載の製造方
法。6. The production method according to claim 4, wherein the polymer having formaldehyde as a constituent unit is a copolymer of formaldehyde and alkylene oxide.
ポキシ環を有する化合物である特許請求の範囲第６項記
載の製造方法。7. The production method according to claim 6, wherein the alkylene oxide is a compound having an epoxy ring having 9 or less carbon atoms.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60198750A JPH0730148B2 (en) | 1985-09-09 | 1985-09-09 | Method for producing polymer having formaldehyde as constitutional unit |
| KR1019860007441A KR930000372B1 (en) | 1985-09-09 | 1986-09-05 | Preparation of Formaldehyde Polymer |
| AT86306884T ATE58149T1 (en) | 1985-09-09 | 1986-09-05 | PROCESS FOR PRODUCTION OF FORMALDEHYDE POLYMERS. |
| EP86306884A EP0217560B1 (en) | 1985-09-09 | 1986-09-05 | Process for preparing polymer of formaldehyde |
| DE8686306884T DE3675488D1 (en) | 1985-09-09 | 1986-09-05 | METHOD FOR PRODUCING FORMALDEHYDPOLYMERS. |
| CA000517655A CA1272841A (en) | 1985-09-09 | 1986-09-08 | Process for preparing polymer of formaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60198750A JPH0730148B2 (en) | 1985-09-09 | 1985-09-09 | Method for producing polymer having formaldehyde as constitutional unit |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6259617A JPS6259617A (en) | 1987-03-16 |
| JPH0730148B2 true JPH0730148B2 (en) | 1995-04-05 |
Family
ID=16396338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60198750A Expired - Lifetime JPH0730148B2 (en) | 1985-09-09 | 1985-09-09 | Method for producing polymer having formaldehyde as constitutional unit |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0217560B1 (en) |
| JP (1) | JPH0730148B2 (en) |
| KR (1) | KR930000372B1 (en) |
| AT (1) | ATE58149T1 (en) |
| CA (1) | CA1272841A (en) |
| DE (1) | DE3675488D1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746602B (en) * | 2019-10-29 | 2021-04-20 | 大连理工大学 | A kind of metal cobalt porphyrin-based porous organic polymer and its preparation method and application |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE758688A (en) * | 1970-11-09 | 1971-05-10 | Angarsky Neftekhimichesky Kom | Trioxane copolymers prepared in the pres- - ence of alkylene carbonates |
| US3803094A (en) * | 1972-07-12 | 1974-04-09 | Ube Industries | Process for producing formaldehyde copolymer |
| JPS54161695A (en) * | 1978-06-13 | 1979-12-21 | Mitsubishi Gas Chem Co Inc | Method of mixing polymerizable materials and device therefor |
-
1985
- 1985-09-09 JP JP60198750A patent/JPH0730148B2/en not_active Expired - Lifetime
-
1986
- 1986-09-05 AT AT86306884T patent/ATE58149T1/en not_active IP Right Cessation
- 1986-09-05 EP EP86306884A patent/EP0217560B1/en not_active Expired - Lifetime
- 1986-09-05 DE DE8686306884T patent/DE3675488D1/en not_active Expired - Lifetime
- 1986-09-05 KR KR1019860007441A patent/KR930000372B1/en not_active Expired - Fee Related
- 1986-09-08 CA CA000517655A patent/CA1272841A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE3675488D1 (en) | 1990-12-13 |
| ATE58149T1 (en) | 1990-11-15 |
| CA1272841A (en) | 1990-08-14 |
| KR870003143A (en) | 1987-04-15 |
| EP0217560A1 (en) | 1987-04-08 |
| KR930000372B1 (en) | 1993-01-16 |
| EP0217560B1 (en) | 1990-11-07 |
| JPS6259617A (en) | 1987-03-16 |
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